WO2001040536A1 - Film mince polycristallin et procede de preparation de ce dernier, oxyde supraconducteur et son procede de preparation associe - Google Patents

Film mince polycristallin et procede de preparation de ce dernier, oxyde supraconducteur et son procede de preparation associe Download PDF

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WO2001040536A1
WO2001040536A1 PCT/JP2000/008420 JP0008420W WO0140536A1 WO 2001040536 A1 WO2001040536 A1 WO 2001040536A1 JP 0008420 W JP0008420 W JP 0008420W WO 0140536 A1 WO0140536 A1 WO 0140536A1
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polycrystalline
thin film
base material
ion beam
polycrystalline thin
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PCT/JP2000/008420
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English (en)
Japanese (ja)
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Yasuhiro Iijima
Mariko Kimura
Takashi Saito
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Fujikura Ltd.
International Superconductivity Technology Center, The Juridical Foundation
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Application filed by Fujikura Ltd., International Superconductivity Technology Center, The Juridical Foundation filed Critical Fujikura Ltd.
Priority to JP2001542599A priority Critical patent/JP3732780B2/ja
Priority to DE60045370T priority patent/DE60045370D1/de
Priority to EP00978005A priority patent/EP1178129B1/fr
Priority to US09/890,052 priority patent/US6632539B1/en
Publication of WO2001040536A1 publication Critical patent/WO2001040536A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00—Superconducting devices
    • H10N60/01—Manufacture or treatment
    • H10N60/0268—Manufacture or treatment of devices comprising copper oxide
    • H10N60/0296—Processes for depositing or forming superconductor layers
    • H10N60/0576—Processes for depositing or forming superconductor layers characterised by the substrate
    • H10N60/0632—Intermediate layers, e.g. for growth control
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G27/00—Compounds of hafnium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
    • C23C18/145—Radiation by charged particles, e.g. electron beams or ion irradiation
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
    • C30B23/002—Controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9265—Special properties
    • Y10S428/93—Electric superconducting
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S505/00—Superconductor technology: apparatus, material, process
    • Y10S505/725—Process of making or treating high tc, above 30 k, superconducting shaped material, article, or device
    • Y10S505/73—Vacuum treating or coating
    • Y10S505/731—Sputter coating

Definitions

  • the present invention relates to a polycrystalline thin film having a pyrochlore-type crystal structure with a well-oriented crystal orientation, a method for producing the same, and an oxide superconducting layer formed on a polycrystalline thin film having a pyrochlore-type crystal structure with a well-oriented crystal orientation.
  • the present invention relates to an oxide superconductor having excellent superconductivity and a method for producing the same. Background art
  • Oxide superconductors discovered in recent years are excellent superconductors that exhibit a critical temperature exceeding the temperature of liquid nitrogen, but at present, this type of oxide superconductor is being used as a practical superconductor. There are various problems to be solved. One of the problems is that the critical current density of oxide superconductors is low.
  • an oxide superconductor having a good crystal orientation is formed on the substrate, and moreover, It is necessary to orient the a-axis or b-axis of the oxide superconductor crystal in the direction in which electricity is to flow, and to orient the c-axis of the oxide superconductor in other directions.
  • oxides than on the intermediate layer have been performed.
  • the oxide superconducting layer formed on this type of intermediate layer by a sputtering device is an oxide superconducting layer formed on a single-crystal substrate made of these materials (for example, a critical current density of 100,000 A). / cm 2 ) which is much lower than the critical current density (for example, about 100 to 100 OA / cm 2 )
  • the critical current density for example, about 100 to 100 OA / cm 2
  • Figure 16 shows an oxide superconducting material in which an intermediate layer 2 is formed on a polycrystalline substrate 1 such as a metal tape by a sputtering device, and an oxide superconducting layer 3 is formed on the intermediate layer 2 by a sputtering device.
  • 3 shows a cross-sectional structure of a conductor.
  • the oxide superconducting layer 3 is in a polycrystalline state, and a large number of crystal grains 4 are in a disordered state. Looking at each of these crystal grains 4 individually, the c-axis of the crystal of each crystal grain 4 is oriented somewhat perpendicular to the substrate surface, but the a-axis and b-axis It is considered suitable.
  • the reason why the oxide superconductor is in a polycrystalline state in which the a-axis and b-axis are not oriented is because the intermediate layer 2 formed thereunder is in a polycrystalline state in which the a-axis and the b-axis are not oriented. This is probably because when the oxide superconducting layer 3 is formed, the oxide superconducting layer 3 grows to match the crystal of the intermediate layer 2.
  • the present inventors previously formed an intermediate layer of YSZ (yttrium-stabilized zirconia) having improved a-axis and b-axis orientation on a polycrystalline base material by using a special method. It has been found that if an oxide superconducting layer is formed on the intermediate layer, an oxide superconducting conductor exhibiting a good critical current density can be manufactured.
  • No. 4 Japanese Patent Application No. 8-2 1 4 8 06, Japanese Patent Application No. 8-2 7 2 6 06, Japanese Patent Application No. 8-2 72 6 07, etc. Has filed a patent application.
  • the technology according to these patent applications is based on the fact that when a film is formed on a polycrystalline base material using a YSZ target, the film is inclined in a direction 50 to 6 with respect to the normal to the film formation surface of the polycrystalline base material.
  • the ion beam assist method which simultaneously irradiates an ion beam such as Ar + at an incidence angle of 0 degrees, YSZ crystals with poor crystal orientation are selectively removed, and YSZ crystals with good crystal orientation are obtained.
  • this technology was able to form an intermediate layer of YSZ with excellent orientation.
  • the a-axis and the b-axis are well oriented.
  • the oxide superconductor formed on this polycrystalline thin film exhibited a good critical current density.
  • FIG. 17 shows a cross-sectional structure of an example of an oxide superconductor recently used by the present inventors.
  • the oxide superconducting conductor D of this example is formed by forming an orientation control intermediate layer 6 of YSZ or MgO on a metal tape base material 5 using the ion beam assist method described above, and then forming Y 20. It has a four-layer structure in which a reaction prevention intermediate layer 7 of No. 3 is formed and an oxide superconducting layer 8 is formed thereon.
  • the YSZ crystal constituting the orientation control intermediate layer 6 has a cubic crystal structure
  • the oxide superconducting layer having a composition of ⁇ , ⁇ a 2 Cu 3 ⁇ 7 - x is a perovskite type.
  • Each of them is a kind of face-centered cubic structure, and has similar crystal lattices, but the difference in lattice size between both crystal lattices is about 5%.
  • nearest interatomic distance 3.63A (0. 363 nm) of the atoms located in the central portion of the surface of the nuclear and cubic lattice located at a corner of the cubic lattice of YS Z, Y 2 0 3 similar distance between nearest atoms is 3.75 a (0.
  • YiB a 2 Cu 3 0 7 - x becomes the same nearest interatomic distance of the oxide superconducting layer of composition 3.81 a (0. 38 in m) in and, Y 2 ⁇ 3 YSZ and Upsilon, beta a 2 Cu 3 ⁇ 7 - exhibits a value between in the chi, also it is advantageous to fill the difference in size of the grid, by Ino near also the composition It is considered to be advantageous as a reaction prevention layer.
  • the four-layer structure shown in FIG. 17 has a problem that the number of necessary layers is large and the number of manufacturing steps is increased.
  • the present inventors conducted research on a material having a crystal structure with good orientation directly on the base material 5 of the metal tape, and having a closest atomic spacing closer to the oxide superconductor than YSYS. As a result, the present invention has been achieved.
  • the present invention has been made to solve the above-mentioned problems, and forms a polycrystalline layer with good orientation on a substrate by applying the ion beam assist method provided by the present inventors.
  • the polycrystalline thin film of the present invention has a composition of either AZrAZ or AHf ⁇ formed on the surface on which the polycrystalline base material is to be formed.
  • A is one rare earth element selected from Y, Yb, Tm, Er, Ho, Dy, Eu, Gd, Sm, Nd, Pr, Ce, and La
  • the relative ratio of the rare earth element to Zr or Hf constituting the polycrystalline thin film of the composite oxide having a pyrochlore type crystal structure represented by either the composition of AZrO or AHf0 is 1: 1. You may.
  • the relative ratio of the rare earth element and Zr or Hf constituting a polycrystalline thin film of a composite oxide having a pi-croe type crystal structure mainly represented by either AZr ⁇ or AHf0 is 0.1. : 0.9 to 0.9: 0.1 and may be cubic.
  • the crystal structure does not always have to be a pyrochlore type, but may have a very similar structure called a defective fluorite type or a rare-earth C type. Even in such a case, it is effective if a cubic crystal is maintained. is there.
  • the polycrystalline substrate composed of a heat-resistant metal tape, such as N i alloys the polycrystalline thin film can be composed of Sm 2 Z r 2 ⁇ 7 or Gd 2 Z r 2 0 7.
  • a grain boundary tilt angle formed by the same crystal axis of each crystal grain of the polycrystalline thin film along a plane parallel to a film formation surface of the polycrystalline base material is set to 20 degrees or less.
  • the method for producing a polycrystalline thin film according to the present invention may have a film forming surface of a polycrystalline substrate in order to solve the above problems. Any composition of AZr0 or AHf0 formed on the above (where A is Y, Yb, Tm, Er, Ho, Dy, Eu, Gd, Sm, Nd, Pr, Ce And one type of rare earth element selected from the group consisting of La and a complex oxide crystal grain having a pi-croh-type crystal structure represented by).
  • a polycrystalline thin film having the same crystal axis of the crystal grains along a parallel plane and having a grain boundary tilt angle of 30 degrees or less
  • the polycrystalline base material is heated to a temperature of 300 ° C. or less, and the ion source is heated.
  • an ion beam to be generated an Ar + ion beam, a Kr + ion beam, a Xe-ten ion beam, or a mixed ion beam thereof is used, and the ion beam energy of the ion beam is 150 eV or more and 300 eV or less.
  • the constituent particles are deposited on the substrate while irradiating the beam at an incident angle of 50 degrees or more and 60 degrees or less with respect to the normal to the film formation surface of the substrate. .
  • the polycrystalline base material is heated to 90 ° C. or more. It is preferable to heat to a temperature of 300 ° C or less, more preferably to a temperature of 150 ° C to 250 ° C, and more preferably to a temperature of 200 ° C. .
  • the ion beam generated from an ion source is It is preferable to adjust the ion beam energy to a range of not less than 175 eV and not more than 225 eV, and more preferably, to not more than 200 eV.
  • the constituent particles when depositing constituent particles generated from an overnight get of a constituent element of the polycrystalline thin film on a polycrystalline base, Preferably, the constituent particles are deposited on the substrate while irradiating at an incident angle of 55 degrees or more and 60 degrees or less with respect to the normal line of the surface on which the film is to be formed, and more preferably the ion beam is applied to the substrate.
  • the constituent particles are preferably deposited on the substrate while irradiating the film at an incident angle of 55 degrees with respect to the normal to the surface on which the film is to be formed.
  • the method for producing a polycrystalline thin film having the above-mentioned structure when depositing constituent particles generated from the target of the constituent element of the polycrystalline thin film on the polycrystalline base material, Heat to a temperature of ° C and use an Ar + ion beam, a K r + ion beam, a Xe + ion beam, or a mixed ion beam of these as the ion beam generated from the ion source.
  • the ion beam energy of the ion beam is adjusted to 200 eV, and the ion beam is irradiated at an incident angle of 55 degrees with respect to the normal to the surface on which the film is formed on the substrate. More preferably, it is deposited on the material.
  • the oxide superconducting conductor of the present invention includes a polycrystalline base material, and AZr ⁇ or AHf ⁇ formed on the surface of the polycrystalline base material on which a film is to be formed.
  • Any composition (where A is Y, Yb, Tm, Er, Ho, Indicates one kind of rare earth element selected from Dy, Eu, Gd, Sm, Nd, Pr, Ce, and La.
  • the grain boundary tilt angle formed by the same crystallographic axis of the crystal grains along the plane parallel to the film-forming surface of the polycrystalline base material which is composed of crystal grains of a composite oxide having a pyrochlore type crystal structure represented by It is characterized by comprising a polycrystalline thin film having a temperature of 30 degrees or less, and an oxide ultra-thin layer formed on the polycrystalline thin film.
  • the oxide than conductive thin layer AiBazCus 0 7 - x, or the composition formula A 2 Ba 4 Cu 8 ⁇ x
  • a in the composition formula is, Y, One kind of rare earth element selected from Yb, Tm, Er, Ho, Dy, Eu, Gd, Sm, Nd, Pr, Ce, and La.
  • a cubic superconductor of another composition may be applied.
  • a heat-resistant metal tape can be used as the polycrystalline base material.
  • the oxide superconducting thin layer has a grain boundary inclination angle of 30 formed by the same crystal axis of the crystal grains along a plane parallel to a film formation surface of the polycrystalline substrate.
  • the degree may be less than the degree.
  • the method for producing an oxide superconducting conductor of the present invention includes: a polycrystalline base; and either AZrO or AHfO formed on a film-forming surface of the polycrystalline base.
  • a particle comprising a composite oxide crystal particle having a pyrochlore-type crystal structure represented by the following, and having the same crystal axis of the crystal particle along a plane parallel to a film-forming surface of the polycrystalline base material.
  • a method for manufacturing an oxide superconducting conductor comprising: a polycrystalline thin film having a field inclination angle of 30 degrees or less; and an oxide superconducting thin layer formed on the polycrystalline thin film, wherein the polycrystalline thin film is
  • the polycrystalline base material The temperature was heated below 300 ° C, as the ion beam I on the source generates, Ar + ion beam, using a Kr + of I O Nbimu, Xe + ion beam, or of mixed ion beam, the ion beam of the ion Beam energy between 150 eV and 300 eV
  • the constituent particles are deposited on the base material while irradiating the ion beam at an incident angle of 50 ° or more and 60 ° or less with respect to the normal to the film-forming surface of the base material, and polycrystalline.
  • the pyrochlore-type polycrystalline film formed on a polycrystalline base material is advantageous in various points over a conventional YSZ polycrystalline thin film when an oxide superconducting layer is provided thereon. Conceivable.
  • the lattice constant of the Z r0 2 consisting mainly in a crystal of YSZ is 5.14A (0. 5 14nm), atoms and the surface you located in the center of the face in the face-centered cubic lattice of the Z r 0 2 If the interval of the atoms located at the corners (nearest interatomic distance) is assumed to be 3.63A (0. 363 nm), S m 2 Z r 2 0 7 lattice constant of crystals of 10.5 9 a (1. 059 nm) at and, nearest interatomic distances 3.74 a (0. 374 nm), and the can nearest interatomic distance of the oxide superconductor of these relative Y!
  • the Sm 2 Z gamma 2 ⁇ 7 is a crystal structure of pyrochlore-type, as other crystal lattice for approximating the crystal structure of pyrochlore-type, Gd 2 Zr 2 0 7 (nearest interatomic distance 3.72 A ( 0. 372 ⁇ m)), L a 2 Z r 2 O 7 ( nearest interatomic distance 3.81 A (0. 381 nm)) , C e 2 Z r 2 0 7 ( nearest interatomic distance 3.78 A (0 . 378 nm)), P r 2 Z r 2 0 7 ( nearest interatomic distance 3.78A (0. 378 nm)), Gd 2 Hf 2 Ov ( recently SeHHara intermolecular distance 3.72A (0.
  • a compound having a pyrochlore type crystal structure represented by any one of the composition formulas can be applied.
  • the relative ratio between the rare earth element and Zr or Hf is not limited to 1: 1 and may be any relative ratio in the range of 0.1: 0.9 to 0.9: 0.1.
  • the crystal structure does not always have to be a pyrochlore type, but may have a very similar structure called a defective fluorite type or a rare earth C type, but in this case, it is effective if the cubic crystal is maintained. .
  • a polycrystalline thin film composed of pyrochlore-type crystal grains such as AZr0 and AHf0 having an excellent crystal orientation with a grain boundary tilt angle of 30 ° or less was formed on a polycrystalline base material. If it is a pyrochlore-type polycrystalline thin film such as SmZr0 having excellent crystal orientation, it is suitable as an underlayer of various thin films formed thereon. If it is a superconducting layer, excellent superconducting characteristics can be obtained. If the thin film to be formed is an optical thin film, it has excellent optical characteristics. If the thin film to be formed is a magnetic thin film, it has excellent magnetic characteristics. If the thin film is a wiring film, a thin film having few wiring resistance and defects can be obtained.
  • Another pyrochlore type composite oxide used for the polycrystalline thin film described above Gd 2 Z r 2 0 Ma, L a 2 Z r 2 O 7S C e 2 Z r 2 0 7, P r 2 Z r 2 0? , Gd 2 H f 2 O 7 , Sm 2 H f 2 ⁇ 7, L a 2 H f 2 0 7 composite oxide represented by any of the composition formula, or, Y 2 Z r 2 ⁇ , Yb 2 Z r 2 ⁇ 7 , ⁇ 2 Z r 2 OTS E r 2 Z r 2 O 7, H o 2 Z r 2 O 7 , Dy 2 Z r 2 0 ?, EU 2 Z r 2 O 7, N d 2 Z r 2 0 ?, Y2 Z r 2 O 7, Y 2 Hf 2 ⁇ 7, Yb 2 Hf 2 0 7 , Tm 2 H f 2 ⁇ 7, E r 2 H f 2 O 7, H o 2 H f 2 O 7
  • a heat-resistant metal tape of Ni alloy is used as the polycrystalline base material used in the present invention.
  • a metal tape provided with a polycrystalline thin film composed of the above-mentioned pi-mouthed crystal grains is used as the polycrystalline base material used in the present invention.
  • the composition of either AZrO or AHf ⁇ Simultaneously with ion beam irradiation when depositing target particles of the pyrochlore-type composite oxide Conditions are 300 ° C or less, ion beam energy is 150 to 300 eV, and the incident angle of the ion beam is 50 to 60 degrees with respect to the normal to the surface on which the film is to be formed. It is possible to obtain a pyrochlore-type composite oxide having a polycrystalline thin film having an excellent grain orientation and an excellent crystal orientation and having an excellent grain boundary tilt angle.
  • any one of AZr ⁇ or AHf0 having excellent crystal orientation as described above (where A is Y, Yb, Tm, Er, Ho, Dy, Eu, Gd, Sm, Nd, Pr, Ce, and La are shown.
  • A is Y, Yb, Tm, Er, Ho, Dy, Eu, Gd, Sm, Nd, Pr, Ce, and La.
  • FIG. 1 is a perspective view showing a cross section of an example of a polycrystalline thin film of a pyrochlore-type composite oxide formed on a substrate by the method of the present invention.
  • FIG. 2 is an enlarged plan view showing crystal grains of the polycrystalline thin film shown in FIG. 1, their crystal axis directions, and grain boundary tilt angles.
  • Figure 3 is a view to conceptual diagram of the crystal lattice of the polycrystalline thin film of pyrochlore type Sm 2 Z r 2 0 7 a composition.
  • FIG. 4 is a configuration diagram showing an example of an apparatus for producing a polycrystalline thin film according to the present invention.
  • FIG. 5A is a configuration diagram showing an example of the ion source of the apparatus shown in FIG.
  • FIG. 5B is an explanatory diagram of the ion beam incident angle.
  • FIG. 6 is a configuration diagram showing an oxide superconducting layer formed on the polycrystalline thin film shown in FIG.
  • FIG. 7 is an enlarged plan view showing crystal grains of the oxide superconducting layer shown in FIG. 6, the crystal axis direction thereof, and the grain boundary tilt angle.
  • FIG. 8 is a configuration diagram showing an example of an apparatus for forming an oxide superconducting layer on the polycrystalline thin film shown in FIG.
  • FIG. 10 a polycrystalline thin film of the composition of Sm 2 Z r 2 0 7 obtained in Example a pole figure of a polycrystalline thin film of Sm 2 Z gamma 2 ⁇ 7 a composition prepared in Example
  • FIG. 6 is a diagram showing the relationship between the incident angle of an ion beam and the crystal orientation at the time of manufacturing the semiconductor device.
  • Figure 11 is a diagram showing the relationship between the substrate temperature and the full width at half maximum in the polycrystalline thin film of Sm 2 Z r 2 0 7 a composition prepared in Example.
  • Figure 12 is a diagram showing the relationship between I O emissions beam energy and the full width at half maximum in the polycrystalline thin film of Sm 2 Z r 2 ⁇ 7 a composition prepared in Example.
  • Figure 13 is a diagram showing a comparison of the full width at half maximum of the polycrystalline thin film of YS Z produced as a comparative example and the full width at half maximum of the polycrystalline thin film of the resulting Sm 2 Z r 2 0 7 a composition in Example 14, YSZ polycrystalline thin film and H f 0 2 polycrystalline thin film and C e ⁇ 2 polycrystalline thin film and Y 2 0 3 polycrystalline thin film and Sm 2 Z ⁇ 2 0? polycrystalline thin film and Gd 2 Z 1 ⁇ ⁇ 7 Polycrystalline thin film?
  • FIG. 4 is a diagram showing the dependence of the value of Ar + ion beam energy on the value of 1 ⁇ 111.
  • Figure 15 is a graph showing by comparison the deposition rate of the G d 2 Z r 2 ⁇ 7 polycrystalline thin film and YSZ polycrystalline thin film.
  • FIG. 16 is a configuration diagram showing a polycrystalline thin film manufactured by a conventional apparatus.
  • FIG. 17 is a cross-sectional view showing an example of a conventional oxide superconductor. BEST MODE FOR CARRYING OUT THE INVENTION
  • FIG. 1 shows an embodiment in which the polycrystalline thin film of the present invention is formed on a substrate.
  • A is a tape-shaped polycrystalline substrate, and B is formed on the upper surface of the polycrystalline substrate A.
  • 3 shows a polycrystalline thin film.
  • the polycrystalline substrate A for example, various shapes such as a plate, a wire, and a tape can be used, and the polycrystalline substrate A is made of N, such as silver, platinum, stainless steel, copper, and hastelloy. It is made of a metal material such as an i-alloy or a heat-resistant material such as various glasses or various ceramics.
  • the crystal grains 20 of the S m 2 Z r 2 0 7 fine crystal aggregate having a pyrochlore-type cubic crystal structure represented by the composition formula is a number, mutual
  • the c-axis of the crystal axis of each crystal grain 20 is oriented at right angles to the upper surface (surface on which the film is formed) of the base material A, and the crystal axis of each crystal grain 20 is formed.
  • the a-axes and b-axes are oriented in the same direction, facing each other in the same direction.
  • the c-axis of each crystal grain 20 is oriented at right angles to the (upper surface) deposition surface of the polycrystalline base material A.
  • the a-axis (or b-axis) of each crystal grain 20 is joined and integrated by setting the angle between them (the grain boundary tilt angle K shown in Fig. 2) within 30 degrees, for example, within the range of 15 to 25 degrees. ing.
  • the crystal lattice of the above-mentioned pi-mouthed chloride complex oxide is derived from a cubic C a F 2 structure, and has eight unit cells having a face-centered cubic structure as shown in FIG.
  • eight oxygen atoms penetrating into the lattice gap formed by the atoms of Sm located at the apex of the unit cell and the atoms of Zr located at the face center of the unit cell Only one of the ⁇ (existing at the position indicated by the dotted line in Fig. 3) is removed to generate an octant, and an I-type octant and a type-II octant are generated according to the position where the oxygen atom is removed.
  • the type I octant and type II octant are regularly arranged to form a pyrochlore crystal lattice.
  • the unit cell is regarded as a unit cell in the field of X-ray analysis when the eight unit cells are overlapped, and the lattice constant of the unit cell is 10.59, but the width of the unit cell is 5.3 A ( 0.53 nm), and the closest interatomic distance is 3.74 A (0.374 nm).
  • the lattice constant 1 0.6 9 Gd 2 Hf 2 O 7 (between nearest interatomic distance 3.72 A (0. 372 nm), the lattice constant 5.2 9), Sm 2 Hf 2 0 7 ( nearest interatomic distance 3 .74 A (0. 374 nm) , the lattice constant 5.2 9) , L a 2 Hf 2 0 7 ( nearest interatomic distance 3.8 1 a (0. 38 1 nm ), the lattice constant 1 0.77) using either a not good.
  • Sm 2 H f 2 0 7 is 5.2 9
  • regularity in the presence of oxygen vacancies is lost Te sheet Nme but birds are believed to have changed
  • the Gd 2 Hf 2 0 7 and Sm 2 Hf 2 0 7 of may be subjected for the purpose of the present invention as viewed from the value of the distance between nearest atoms of course It is.
  • Y 2 Zr 2 ⁇ 7 nearest interatomic distance 3.67 A (0.367 nm), lattice constant The number 5.19
  • Yb 2 Zr 2 0 7 nearest interatomic distance 3.66 A (0. 366 nm), the lattice constant 5.17
  • Tm 2 Z r 2 O 7 nearest interatomic distance 3.66 A (0. 366 ⁇ m)
  • the lattice constant 5.17 E r 2 Z r 2 0 7 ( nearest interatomic distance 3.67 ⁇ (0. 3 67 nm), the lattice constant 5.19)
  • Ho 2 Zr 2 0 7 nearest interatomic distance 3.68 A
  • the lattice constant of the oxide superconductor is 3.81 and the closest atomic distance is 3.81 A (0.381 nm), and it is particularly close to the closest atomic distance of 3.81 A (0.381 nm).
  • the relative ratio of Zr or Hf is not limited to 1: 1. Any relative ratio within the range of 0.1: 0.9 to 0.9: 0.1 can be employed.
  • the crystal structure does not always have to be a pyrochlore type, but may have a very similar structure called a defective fluorite type or a rare earth C type, but in this case, it is effective if the cubic crystal is maintained. .
  • FIG. 4 shows an example of an apparatus for producing the polycrystalline thin film B.
  • the apparatus in this example has a configuration in which an ion source for ion beam assist is provided in a sputter device.
  • the apparatus of this example includes a base material holder 23 that supports the tape-shaped polycrystalline base material A and can heat it to a desired temperature, and a tape-shaped polycrystalline base material A on the base material holder 23.
  • a plate-shaped evening beam 36 which is arranged at a predetermined distance from each other, and a spark beam irradiating device 38, which is arranged diagonally above the evening gate 36 and faces the lower surface of the evening gate 36.
  • the target 36 and the ion source 39 which is opposed to the side of the substrate holder 23 at a predetermined interval and is spaced apart from the target 36, are placed in a film-forming processing container 40 capable of evacuating. It is a schematic configuration accommodated.
  • the substrate holder 23 is provided with a heating heater inside, so that the tape-shaped polycrystalline substrate A sent out onto the substrate holder 23 can be heated to a desired temperature as required. ing.
  • the substrate holder 23 is rotatably mounted on the support 23a by pins or the like. It is attached, and the inclination angle can be adjusted. Such a substrate holder 23 is disposed in an optimum irradiation area of the ion beam irradiated from the ion source 39 in the film forming processing container 40.
  • a tape-shaped polycrystalline base material A is continuously fed from the base material delivery bobbin 24 onto the base material holder 23, and a polycrystalline thin film is formed in the optimum irradiation region.
  • a polycrystalline thin film is formed in the optimum irradiation region.
  • the evening get 36 is for forming a target polycrystalline thin film, and has the same composition or a similar composition as the target polycrystalline thin film.
  • the evening specifically as an rodents DOO 36, Sm 2 Z r 2 0 7, Gd 2 Zr 2 ⁇ 7, La 2 Z r 2 ⁇ 7, Ce 2 Z r 2 ⁇ 7, P r 2 Z r 2 O 7 , G d 2H f 2 O 7 , Sm 2 Hf 2 0 7, L a 2 H f 2O 7 either the target of the composite oxide represented by the composition formula or, of these individual three constituent elements
  • a target having a composition containing a large amount of elements which are easily scattered when it is formed into a film is used.
  • Such a target 36 is attached to a target support 36a, which is held by a pin or the like in a rotating manner, so that the inclination angle can be adjusted.
  • composition pyrochlore type complex oxide represented by the formula Xi may be employed over g e t and.
  • the relative ratio between the rare earth element and Zr or Hf is not limited to 1: 1 but may be any relative ratio in the range of 0.1: 0.9 to 0.9: 0.1.
  • Targets can be adopted as appropriate.
  • the crystal structure is not necessarily a pyrochlore type, but a force that may take a very similar structure called a defective fluorite type or a rare earth C type; even in this case, it is effective if a cubic crystal is maintained. is there.
  • the sputter beam irradiation device (spa means) 38 In this way, the constituent particles of the target 36 can be beaten toward the polycrystalline base material A by irradiating an ion beam.
  • the ion source 39 has substantially the same configuration as the sputter beam irradiation device 38, is provided with a pipe for introducing gas into the ionization chamber, and is provided with a grid for applying an extraction voltage. I have.
  • This device ionizes some of the atoms or molecules of the introduced gas, and irradiates the ionized particles as an ion beam under the control of an electric field generated by the grid.
  • There are various methods for ionizing particles such as a DC discharge method, a high-frequency excitation method, and a filament method.
  • the filament type is a method in which a tungsten filament is energized and heated to generate thermoelectrons, which are then collided with evaporated particles in a high vacuum to be ionized.
  • an ion source 39 having the internal structure shown in FIG. 5A is used.
  • the ion source 39 is provided with a grid 46, a filament 47, and an inlet tube 48 for Ar gas, Kr gas, Xe gas or the like inside a cylindrical ion chamber 45.
  • the ion beam can be emitted from the beam port 49 at the tip of the ion chamber 45 almost parallel to the beam.
  • the ion source 39 has a central axis S with respect to the upper surface (deposition surface) of the polycrystalline base material A at an incident angle 6> (deposition of the polycrystalline base material A). They are inclined and opposed by the perpendicular (normal) H of the surface (upper surface) and the center line S.
  • the incident angle 0 is preferably in the range of 50 to 60 degrees, more preferably in the range of 55 to 60 degrees, and most preferably about 55 degrees. Therefore, the ion source 39 is arranged so as to be able to irradiate the ion beam at a certain incident angle 6> with respect to the normal H of the film-forming surface of the polycrystalline base material A.
  • the angle of incidence of such an ion beam relates to the technology for which the present inventors have previously applied for a patent.
  • the ion beam applied to the polycrystalline base material A by the ion source 39 is an Ar gas ion beam, a Kr gas ion beam, a Xe gas ion beam, or these Ar gas and K A mixed ion beam of two or more combinations of r gas and Xe gas, for example, a mixed ion beam of Ar gas and Kr gas can be used.
  • the inside of the container 40 is set to a low pressure state such as a vacuum.
  • a cryopump 52 and an atmospheric gas supply source such as a gas cylinder are connected to each other, and the inside of the film forming vessel 40 is kept in a low pressure state such as a vacuum, and Argon gas or other inert gas atmosphere can be used.
  • the film formation processing container 40 includes a current density measuring device for measuring the current density of the ion beam in the container 40, and a pressure gauge 5 for measuring the pressure in the container 40. 5 is installed.
  • the tilt angle can be adjusted by rotatably attaching the substrate holder 23 to the support 23 a with a pin or the like.
  • An angle adjusting mechanism may be attached to the supporting portion of the ion source to adjust the inclination angle of the ion source 39 so that the incident angle of the ion beam can be adjusted.
  • the angle adjusting mechanism is not limited to this example. Of course, various configurations can be adopted.
  • Next the case of forming a polycrystalline thin film B of the pi port Kuroa type of the aforementioned compositions, such as S m 2 Z r 2 0 7 will be described on the polycrystalline substrate A using an apparatus of the configuration.
  • a target 36 made of the above-described complex oxide is used, and a film forming processing vessel 40 containing the polycrystalline base material A is used.
  • the inside of the chamber is evacuated to a reduced-pressure atmosphere, and the polycrystalline base material A is sent out from the base material delivery bobbin 24 to the base material holder 23 at a predetermined speed, and further irradiated with the ion source 39 and the spark beam. Activate device 38.
  • the constituent particles of the target 36 are beaten out and fly onto the polycrystalline base material A.
  • the constituent particles struck out from the evening target 36 are deposited, and simultaneously from the ion source 39, for example, A r + ion of the ion beam, K r + ions of the ion beam, an ion beam of X e + ions, Or, by irradiating a mixed ion beam of K r + and X e + ions forming a polycrystalline thin film having a desired thickness
  • the tape-shaped polycrystalline substrate A after film formation is wound around a substrate winding bobbin 25.
  • the incident angle 0 when irradiating the ion beam is preferably in a range of 50 degrees or more and 60 degrees or less, and most preferably 55 degrees.
  • the c-axis of the above-mentioned polycrystalline thin film of the composite oxide will not be oriented.
  • 0 is set to 30 degrees, the above-mentioned polycrystalline thin film of the composite oxide does not even have c-axis orientation. If the ion beam is irradiated at an incident angle in the preferable range as described above, the c-axis of the crystal of the polycrystalline thin film of the composite oxide will be raised.
  • the a-axis and the b-axis of the crystal axes of the polycrystalline thin film of the composite oxide formed on the polycrystalline base material A are in the same direction as each other.
  • In-plane orientation can be performed along a plane parallel to the upper surface (deposition surface) of the polycrystalline base material A.
  • the temperature of the polycrystalline base material A and the ion beam energy of the assist ion beam are set within a specified range in addition to the irradiation angle of the assist ion beam. It is preferable to set.
  • the temperature of the polycrystalline base material A is preferably formed while heating to an appropriate temperature of 300 ° C. or less, and the grain boundary tilt angle is set to 25 ° or less based on the results of the examples described later.
  • the temperature is preferably 90 ° C or more and 300 ° C or less, and even within this range, 150 ° C or more and 250 ° C to ensure the grain boundary inclination angle of 20 ° or less.
  • the following range is more preferable, and 200 ° C. is most preferable.
  • the temperature of 90 ° C is the temperature at which the substrate is naturally heated by the ion beam irradiating the substrate and the residual heat of the device, even if the substrate is not specially heated, at room temperature. is there.
  • the ion beam energy is preferably 150 eV or more and 300 eV or less in order to make the grain boundary inclination angle 30 degrees or less, but it is 17 7 in order to make the grain boundary inclination angle 20 degrees or less.
  • the range is preferably 5 eV or more and 225 eV or less, more preferably 200 eV.
  • a polycrystalline thin film B such as a pi-crotch type can be formed with good orientation. it can.
  • FIG. 1 shows a S m 2 Z r 2 0 7 polycrystalline substrate A polycrystalline thin film B of the composite oxide is deposited in the above, such as in the manner described.
  • FIG. 1 shows a state in which only one crystal grain 20 is formed, the crystal grain 20 may of course have a multilayer structure. It is. Note that the present inventors assume the following as a factor for adjusting the crystal orientation of the polycrystalline thin film B.
  • Unit cell of the crystal of the polycrystalline thin film B of S m 2 Z r 2 0 7 is a pyrochlore structure of face-centered cubic system of isometric system as shown in FIG. 5 B, in the crystal lattice,
  • the normal direction of the substrate is the ⁇ 100> axis
  • the other ⁇ 110> axes are the directions shown in FIG. 5B.
  • the diagonal direction of the unit cell with respect to the origin ⁇ in Fig. 5B, that is, along the ⁇ 111> axis Incident angle is 54.7 degrees.
  • exhibiting a good crystal orientation in the range of the incident angle of 50 to 60 degrees means that the incident angle of the ion beam coincides with or is about 54.7 degrees.
  • ion channeling occurs most effectively, and in the crystals deposited on the polycrystalline base material A, only atoms that are stable on the upper surface of the polycrystalline base material A due to the arrangement relationship corresponding to the angle described above. It is easy to remain selectively, and other unstable atomic arrangements are sputtered and removed by the ion beam sputtering effect.As a result, only crystals with well-oriented atoms are selectively selected. It is presumed that they will remain and accumulate in the area.
  • FIG. 6 and FIG. 7 show one embodiment of the oxide superconductor according to the present invention.
  • the oxide superconductor 22 of the present embodiment includes a tape-shaped polycrystalline base material A, It comprises a polycrystalline thin film B formed on the upper surface of the polycrystalline base material A, and an oxide superconducting layer C formed on the upper surface of the polycrystalline thin film B.
  • the polycrystalline base material A and the polycrystalline thin film B are composed of the same material as the material described in the previous example, and the crystal grains 20 of the polycrystalline thin film B have grain boundaries as shown in FIG. 1 and FIG.
  • the crystal is oriented so as to have an inclination of 25 degrees or less, preferably 17 to 20 degrees.
  • the oxide superconducting layer C which has been coated on the upper surface of the Sm 2 Z r 2 0?
  • the a-axis and the b-axis of the crystal grains 21 are oriented in a plane parallel to the upper surface of the base material in the same manner as in the case of the polycrystalline thin film B described above.
  • the grain boundary inclination angle K formed by each other, is set within 30 degrees.
  • the oxide superconductor constituting this oxide superconducting layer is Y! Baz Y 2 B a 4 CueOx, Y 3 Ba 3 Cu 6 ⁇ x , or (B i, P b) 2 C a 2 S r 2 Cu 3 Ox, (B i, P b) 2 C a 2 S r 3 Cu 4 ⁇ x , or T l 2 B a 2 C a 2 Cu 3 O x , T 1 i B a 2 C a 2 CuaOx, T 1, B a 2 C a 3 C u 4 ⁇ x
  • it is an oxide superconductor having a high critical temperature typified by such a composition as described above it is a matter of course that other oxide-based superconductors in this example may be used.
  • the oxide superconducting layer C is formed, for example, on the polycrystalline thin film B by a film forming method such as sputtering and laser vapor deposition, and the oxide superconducting layer laminated on the polycrystalline thin film B is also used. Since sm 2 Z r 2 ⁇ deposited to match the orientation of the polycrystalline thin film B of the pyrochlore type composite oxide, such as 7, the oxide superconducting layer formed on the polycrystalline thin film B, the crystal grain excellent quantum binding in the field, because there is little deterioration of superconducting properties at the crystal grain boundary, easily passed, the electrolysis in the longitudinal direction of the polycrystalline substrate a, M gO and S r T0 3 single crystal substrate Sufficiently high critical current density is obtained, which is comparable to that of the oxide superconducting layer obtained by forming it on top.
  • a film forming method such as sputtering and laser vapor deposition
  • the material of the polycrystalline thin film beta preferably towards the pyrochlore type composite oxide such as Sm 2 Z r 2 0 7 than YSZ, provided an oxide superconducting layer on a polycrystalline thin film of for YS Zeta than things, towards the Sm 2 Z r 2 ⁇ 7 pyrochlore multi crystal thin film, such as those provided an oxide superconductor layer is excellent in crystal orientation, at elevated temperature (7 0 0 ⁇ 8 0 0 ° C ) It is resistant to heat treatment and exhibits an excellent critical current density equal to or better than that provided on a YSZ polycrystalline thin film, and has a stable orientation, which is advantageous for maintaining high characteristics during long-length synthesis.
  • heat treatment such as heat treatment Even after passing through, it is possible to obtain a superconducting conductor having a low critical current density and a high critical current. The reason is considered to be due to the following explanation.
  • pie port such as S m 2 Z ⁇ 2 ⁇ 7 having a nearest interatomic distance close to the oxide superconducting layer in terms of nearest interatomic distance than polycrystalline thin film of YSZ This is because a polycrystalline thin film of a chlor-type composite oxide is more advantageous in terms of crystal consistency, and an oxide superconducting layer having more excellent crystal orientation is easily formed.
  • the selection range of the ion beam energy during the film formation and the selection temperature range during the film formation can be broadly selected. A stable crystal orientation can be obtained even if the conditions vary somewhat in the film.
  • FIG. 8 shows an example of an apparatus for forming an oxide superconducting layer by a film forming method
  • FIG. 8 shows a laser vapor deposition apparatus.
  • the laser vapor deposition apparatus 60 of this example has a processing vessel 61, and a tape-shaped polycrystalline substrate ⁇ and a target 63 can be set in a vapor deposition processing chamber 62 inside the processing vessel 61. ing. That is, a base 64 is provided at the bottom of the vapor deposition processing chamber 62, and the polycrystalline base material A can be set on the upper surface of the base 64 in a horizontal state. An evening target 63 supported diagonally upward by a support holder 66 is provided in an inclined state, and the polycrystalline base material A is sent out from a drum-shaped tape feeding device 65 a to a base 64, and this is fed to a drum. It is configured such that it can be wound on a tape-shaped winding device 65a.
  • the processing container 61 is connected to a vacuum exhaust device 67 through an exhaust hole 67a so that the inside can be depressurized to a predetermined pressure.
  • the target 63 has a composition similar or similar to that of the oxide superconducting layer C to be formed, or a composite oxide sintered body containing many components that easily escape during film formation. It is made of a plate such as a superconductor.
  • the base 64 incorporates a heater, and heats the polycrystalline substrate A to a desired temperature. You can heat up.
  • a laser light emitting device 68 a first reflecting mirror 69, a condenser lens 70 and a second reflecting mirror 71 are provided on the side of the processing container 61, and the laser light emitting device 68
  • the laser beam can be focused and irradiated on the evening target 63 through a transparent window 72 attached to the side wall of the processing container 61.
  • any device such as a YAG laser or an excimer laser may be used as long as it can strike out constituent particles from the evening target 63.
  • a laser vapor deposition device 60 shown in FIG. 8 is used.
  • the polycrystalline base material A on which the polycrystalline thin film B is formed is placed on a base 64 of a laser vapor deposition device 60 shown in FIG. 8, and the pressure in the vapor deposition processing chamber 62 is reduced by a vacuum pump.
  • an oxygen gas may be introduced into the vapor deposition processing chamber 62 to make the vapor deposition processing chamber 62 an oxygen atmosphere.
  • the heating heater of the base 64 is operated to heat the polycrystalline base material A to a desired temperature.
  • the laser beam generated from the laser light emitting device 68 is focused and irradiated on the evening target 63 of the evaporation processing chamber 62.
  • the constituent particles of the target 63 are extracted or evaporated, and the particles are deposited on the polycrystalline thin film B.
  • S m 2 Z ⁇ 2 0 7 of polycrystalline thin film B are oriented in advance c-axis during the sedimentary structure particles, since the orientation in the a-axis and b-axis, is formed on the polycrystalline thin film B
  • the c-axis, a-axis, and b-axis of the crystal of the oxide superconducting layer C are also epitaxially grown and crystallized so as to match the polycrystalline thin film B.
  • nearest interatomic distance of the polycrystalline thin film B of S m 2 Z r 2 ⁇ 7 3 7 is 4 A, Y, B a 2 C u 3 0 7 -.
  • the oxide superconducting layer C formed on the polycrystalline thin film B is in a polycrystalline state, In each of the crystal grains of the oxide superconducting layer C, as shown in FIG. 6, the c-axis, through which electricity does not easily flow, is oriented in the thickness direction of the polycrystalline base material A, and the length of the polycrystalline base material A is elongated. The a-axis or b-axis are oriented in the direction. Therefore, the obtained oxide superconducting layer has excellent quantum coupling properties at the crystal grain boundaries and little deterioration of superconducting properties at the crystal grain boundaries, so that electricity can easily flow in the plane direction of the polycrystalline base material A, and the critical current density can be reduced. Excellent results are obtained. In order to further stabilize the crystal orientation and film quality of the superconducting layer C, it is preferable to perform a heat treatment of heating to 700 to 800 ° C for a necessary time and then cooling.
  • Figure 4 Using the apparatus for producing a polycrystalline thin film having the structure shown in, 399.9 x 1 by evacuating the internal deposition process container mouth Isseki Riponpu and cryopump of the manufacturing apparatus 0 - 4 P a (3.0 X 1 0 pressure was reduced to 4 Torr).
  • HASTELLOY C 276 tape having a width of 10 mm, a thickness of 0.5 mm, and a length of 100 cm and having a mirror-polished surface was used.
  • the target is used as the Sm 2 Z r 2 0 7 consisting manufactured composite oxide of the composition, sputtering evening voltage 1 000 V, sputtering evening current 100 mA, an incident angle of A r + ion beam generated from the ion source
  • the temperature was set to 55 degrees with respect to the normal to the film deposition surface of the substrate, the transport distance of the ion beam was set to 40 cm, the assist voltage of the ion source was set to 200 eV, and the temperature of the substrate tape was set.
  • the incident angle of the ion beam in the ion beam assist method was set to 50 degrees. If it is less than 60 degrees, it can be easily presumed that even if the incident angle is set to more than 60 degrees, an intermediate layer having good orientation cannot be obtained.
  • the full width at half maximum of the sample formed at 200 ° C was 17.1 ° C, which was the best. From the relationship shown in Fig. 11, the value of the full width at half maximum, in other words, in order to ensure the grain boundary inclination angle to 25 degrees or less, it is necessary to set the temperature to 100 degrees C or more and 300 degrees C or less, It is clear that the deposition temperature must be set at 150 ° C or higher and 250 ° C or lower to ensure that the grain boundary tilt angle is 20 ° or lower.
  • FIG. 12 shows the result of measuring the full width at half maximum of the polycrystalline thin film of Sm 2 Z r 2 0 7 for each ion beam energy. Other conditions are the same as those of the test described first.
  • the ion beam energy of 150 eV or more and 300 eV or less was selected to make the grain boundary tilt angle of the polycrystalline thin film of Sm 2 Z ⁇ 2 ⁇ 7 30 degrees or less. It has been found that the ion beam energy must be in the range of 175 eV or more and 225 eV or less to ensure that the tilt angle is 20 degrees or less.
  • FIG. 5 shows the ion beam energy dependence in the case of the comparison.
  • one than the grain boundary inclination angle of the polycrystalline thin film of it is YS Z of the grain boundary inclination angle of the polycrystalline thin film of Sm 2 Z r 2 0 7 which method produced using the present invention the ion A low value is also obtained for the beam energy. From the test results, towards the polycrystalline thin film of Sm 2 Z r 2 ⁇ even with variations in the ion beam energy during manufacture if it is shown that easy to manufacture. This means that high Sm 2 Z r 2 0 7 stability it is difficult to constraints conditions during manufacture of the polycrystalline thin film than the polycrystalline thin film of YS Z. Next, to form an oxide superconducting layer using the laser deposition apparatus shown in FIG.
  • a target composed of an oxide superconductor having a composition of YiBazCusO x was used as an evening target.
  • the pressure inside the evaporation chamber was reduced to 26.6 Pa (2 ⁇ 10 1 Torr), and laser evaporation was performed at a substrate temperature of 700 ° C.
  • a KrF excimer laser with a wavelength of 248 nm was used as a laser for evening evaporation.
  • heat treatment was performed at 400 ° C. for 60 minutes in an oxygen atmosphere.
  • the resulting oxide superconductor is 1.0 cm wide and 100 cm long. This oxide superconducting conductor was immersed in liquid nitrogen, and the critical current density was determined for the 10 mm wide and 1 Omm long central part by the four-terminal method.
  • the polycrystalline thin films of any composition have some degree of grain boundary tilt angle, they have excellent orientation in the polycrystalline thin films of any of the composite oxides. It turned out that the nature was obtained. Moreover, I also at 1 50 e V ⁇ 300 e ion beam energy between V in Sm 2 Z r 2 ⁇ 7 polycrystalline thin film and Gd 2 Z r 2 0 7 have shifted the polycrystalline thin film according to the present invention O It is understood that assisting is preferable, and the range of 150 to 250 eV is more preferable, and 200 eV is most preferable.
  • FIG. 4 is a diagram illustrating a relationship between a value and a film forming time. Other conditions are the same as the previous example.
  • ⁇ is the full width at half maximum
  • A is the constant depending on the initial conditions.
  • the ability to form a film in such a short time is an advantageous condition when manufacturing a long oxide superconductor, and even when manufacturing a long oxide superconductor, the manufacturing time is reduced. It can be shortened, and has the effect of reducing manufacturing costs.
  • the full width at half maximum of the YSZ polycrystalline thin film shown in Fig. 15 converges to 13 to 15 ° by forming the film for 6 to 8 hours, and the YSZ polycrystalline thin film disclosed by The value is better than the orientation. This is due to the optimization of ion beam energy and the film formation temperature, and the improvement of the equipment, which allows longer sputter time.

Abstract

La présente invention concerne un film mince polycristallin (B) qui est formé sur une surface destinée à comporter un film en substrat polycristallin (A) et qui comprend un oxyde composite à système cubique dont la composition est représentée par AzrO ou AHfO, où A représente un élément sélectionné parmi Y, Yb, Tm, Er, Ho, Dy, Eu, Gd, Sm, Nd, Pr, Ce et La et qui présente une structure cristalline du type pyrochrore, dans laquelle les axes des grains cristallins respectifs dans le film mince polycristallin formé sur la surface devant comporter un film polycristallin constitué d'un substrat polycristallin (A) présentent un angle d'inclinaison des joints de grains qui est inférieur ou égal à 30° entre ces derniers.
PCT/JP2000/008420 1999-11-29 2000-11-29 Film mince polycristallin et procede de preparation de ce dernier, oxyde supraconducteur et son procede de preparation associe WO2001040536A1 (fr)

Priority Applications (4)

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JP2001542599A JP3732780B2 (ja) 2000-05-29 2000-11-29 多結晶薄膜とその製造方法および酸化物超電導導体とその製造方法
DE60045370T DE60045370D1 (de) 1999-11-29 2000-11-29 Polykristalliner dünner film und verfahren zu dessen herstellung, und supraleitendes oxid und verfahren zu dessen herstellung
EP00978005A EP1178129B1 (fr) 1999-11-29 2000-11-29 Film mince polycristallin et procede de preparation de ce dernier, oxyde supraconducteur et son procede de preparation associe
US09/890,052 US6632539B1 (en) 1999-11-29 2000-11-29 Polycrystalline thin film and method for preparing thereof, and superconducting oxide and method for preparation thereof

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JP33873199 1999-11-29
JP11/338731 1999-11-29
JP2000159249 2000-05-29
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Cited By (2)

* Cited by examiner, † Cited by third party
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WO2008123441A1 (fr) 2007-03-29 2008-10-16 Fujikura Ltd. Film mince polycristallin et son procédé de fabrication et oxyde supraconducteur
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US6632539B1 (en) 2003-10-14

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